Emulsifiable oil



United States Patent EMULSIFIABLE OIL Thomas H. Cafcas, Chicago, Ill., and John J. Plemich, Whiting, Ind., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application August 29,v 1955 Serial No. 531,276

4 Claims. (Cl. 252-33.4)

This invention relates to an emulsifiable oil and more particularly to a soluble oil for use as a non-ferrous, metal-rolling lubricant.

Emulsifiable, non-ferrous" metal-rolling lubricants, and particularly brass-rolling lubricants, are soluble oils having adequate lubricity to prevent sticking and/or burnishing of the metal sheets as they pass between the rolls. Such lubricants are applied as emulsions with water to oil ratios in the range of from about 1:1 to as high as 20:1. In addition to having adequate lubricity, these oils must not leave a deposit that will cause the nonferrous metal to stain in subsequent handling, for instance, in annealing steps and the like. Another characteristic, or property, which these oils must have, particularly when rolling brass or copper, is a minimum tendency to form copper soaps which tend to reduce the stability of the emulsion.

Soluble oils of conventional composition, as taught by the prior art, cause appreciable staining of non-ferrous metals, and particularly brass, in annealing operations subsequent to the rolling operations. Such oils generally comprise petroleum sulfonates, rosin soaps and/or fatty acid soaps in a hydrocarbon oil base.

Many attempts have been made to formulate compositions which provide adequate lubricity in the aforementioned rolling operations while preventing staining of brass and the like as occurs when compositions as set forth above are used. It has recently been discovered that using a non-ionic emulsifier in a hydrocarbon oil in the presence of a minor amount of water provides such a composition useful for providing adequate lubricity and preventing sticking and/or burnishing of non-ferrous metal. It is essential that water be present at all times and in some instances that a coupling agent be present to maintain the non-ionic emulsifier in solution with the hydrocarbon oil. It is a primary object of this invention to provide an improved emulsifiable lubricant. It is a further object to provide a soluble oil which may be used as a lubricant in rolling non-ferrous metals. Another object is to provide a non-ferrous, metal-rolling lubricant which is stable in the absence of water. A more particular object is to provide a brass-rolling lubricant which will not stain brass in annealing steps subsequent to rolling operations. Another object is to provide a rolling lubricant for brass having a minimum tendency to form copper soaps.

The objects of the invention are accomplished by providing an emulsifiable oil consisting of a major portion of a hydrocarbon oil, a minor portion of an unsaturated fatty acid, a minor portion of an alkyl aryl polyether alcohol and a minor portion of a polyoxyethyl ester of un- The alkyl aryl polyether alcohol is "ice about /1o%' to about 15%; the polyoxyethyl group may have from about 8 to 24 carbon atoms and the unsaturated fatty acid may have from about" 8 to about 24 carbon atoms. The oil soluble sulfonates which may be present may be employed in the range of from about 0.0l% to about 1%. The number of carbon atoms in the sul'fonatev is not critical except that it must be oil soluble.

A suitable hydrocarbon oil which may be used in the" composition is a petroleum oil having a viscosity in the range of from about 50 to about 600 SSU at F. Other oleaginous compounds, may be used provided that they have adequate lubricating properties. For instance, a fatty oil, such as lard oil, and others well known to those skilled in the art may be used.

The unsaturated fatty acids used in the invention may' be obtained naturally or synthetically, forinstance, they may be obtained by saponifying certain natural fats.

The alkyl aryl polyether alcohols which are used in the invention may be prepared by any conventional method. However, it is preferred to prepare them by condensation -of ethylene oxide and an alkylated phenol having a lateral chain of from about 8 to about 16 carbon atoms. The substituted phenols may be reacted with from about 4 to about 20 mole of ethylene oxide.

The polyoxyethyl ester of unsaturated fatty acid which is used in the invention may be prepared by reacting single or mixed polyoxyethyl alcohols with single or mixed unsaturated fatty acids using any of the techniques well known to those skilled in the art. The alcohols maybe completely esterified or only partially esterified. It is preferable, however, to use slightly less than an equivalent amount of fatty acid thereby producing a partially esterified reaction product. Polyoxyethyl alcohols having from about 8 to about 24 carbon atoms may beused in this reaction. They may be prepared by conventional polymerization of alkylene oxides such as ethylene oxide to produce the desired polyoxyethyl alcohol. The fatty acids may be obtained synthetically or naturally as pointed out hereinbefore; the molecular weight of such fatty acids should be in the range of from about 12 to about 40 carbon atoms and preferably between about 16 and about 24 carbon atoms.

The oil soluble sulfonates which may be incorporated in the composition may be obtained by any of the conventional methods. For example, one of the preferablev and. more economical methods of obtaining the sulfonates is in the treating of hydrocarbon oils, such as mineral or petroleum oils, with strong sulfuric acid, such as concentrated or fuming sulfuric acid. In the treatment of petroleum oils to obtain highly refined products such as technical white oils, medicinal white oils, turbine oils, etc., the petroleum oils are treated successively with a number of portions of. concentrated sulfuric acid or fuming sulfuric acid. A variety of sulfur containing compounds are thus formed. Most of these compounds are relatively oil insoluble and are separated. from the oil along with the unreacted sulfuric acid. Some of. the sulfonic acids resulting from the treatment of the oil with sulfuric acid are preferentially oil soluble and remain in the oil layer after removal of the acidsIudge. The salts of such sulfonic acids can be obtained by neutralizing the acid treated oil With basic alkali metal compounds, such as basic salts of sodium, potassium or lithium, to form sulfonates which may then be ex-.

3 tracted from the oil by treatment with 50% to 80% aqueous alcohol solutions or other suitable means.

In preparing the metal sulfonates, which are useful in the invention, from the petroleum sulfonic acids, we can use substantially oil-free sulfonic acids, although, for practical purposes, blends of oils and sulfonie acids can be used. Usually, sulfonic acids are recovered as blends of about 40-50% sulfonic acid in hydrocarbon oil.

Inasmuch as full scale production tests rarely can be run on lubricants of this type because they are both costly and time consuming and because production equipment is seldom available for test purposes, a laboratory test has been evolved to evaluate such lubricants. Such a test is described in great detail in Lubrication Engineering, May-June 1954, pages 147-150. This test consists essentially of drawing a wire through a die under closely controlled conditions while measuring the work done in such drawing operation. Such a test was carried out on the following compositions:

1% reaction product of one mol of dodecyl phenol and 12 mols of ethylene oxide 2% reaction product of one mol of nonyl phenol with 4.5 mols of ethylene oxide 2% oleic acid 6.7% reaction product of mixed fatty acids and polyoxyethyl alcohols obtained by polymerizing ethylene oxide, which esterified product has an API gravity of 12.4, an SSU viscosity at 100 F. of 175 seconds,

.a neutralization number of 10.23 mg. KOH/gm., a

saponification number of 95, and an iodine number of 70 0.4% sodium neutralized oil soluble sulfonic acid 88% refined paraffin oil having a viscosity of 55 SSU at 0.25% bactericide 0.5% triethanolamine 1% water 4% sodium rosin soap 29% purified petroleum sulfonate (50% in oil) 65.25% refined petroleum oil having a viscosity of 140 SSU at 100 F.

TABLE I Drawing Copper Stain Lubricant (4:1 emulsion) Work, Rating foot-pounds A 485 None-slight. B 536 Severe.

Lubricant A is illustrative of the novel rolling lubricants of this invention. Lubricant B is typical of the prior art compositions. It is to be noted that lubricant A requires less drawing work than lubricant B and that the tendency to stain copper is practically negligible with lubricant A whereas with lubricant B stain is quite severe.

Percentages given herein and in the appended claims are by weight based upon the total lubricant composition unless otherwise specified.

The soluble oils having the composition set forth hereinbefore may be diluted with water in the proportion of one part of oil to one to twenty parts of water and satisfactory rolling lubricants obtained.

Having thus described our invention, what we claim as novel and desire to protect by Letters Patent is as follows:

1. A non-staining emulsifiable oil for the working of copper-containing non-ferrous metals consisting of a major portion of a hydrocarbon oil; from about 0.1% to about 10% by weight of an alkyl aryl polyether alcohol, wherein said alkyl group has from about 8 to about 16 carbon atoms and said polyether alcohol group has from about 8 to about 40 carbon atoms; from about 0.1% to about 15% by weight of a polyoxyethyl ester of unsaturated fatty acid, wherein said polyoxyethyl group has from about 8 to about 24 carbon atoms and said unsaturated fatty acid has from about 16 to about 24 carbon atoms; and from about 0.1% to about 10% weight of oleic acid.

2. The composition of claim 1 having included therein from about 0.01% to about 1% of an oil soluble sulfonic. acid having an alkali metal constituent.

3. A non-staining emulsifiable oil for the working of copper-containing non-ferrous metals consisting of a major portion of a petroleum oil; from about 0.5% to about 5% by weight of dodecyl phenyl polyether alcohol wherein said polyether alcohol group has about 24 carbon atoms; from about 0.5% to about 5% by weight of nonyl phenyl polyether alcohol wherein said polyether alcohol group has about 9 carbon atoms; from about 0.1% to about 15% by weight of mixed polyoxyethyl esters of mixed fatty acids wherein said polyoxyethyl groups are prepared by the polymerization of ethylene oxide and have from about 10 to about 20 carbon atoms and said mixed fatty acids have from about 16 to about 24 carbon atoms, and said esterified product has an API gravity of about 12, an SSU viscosity at F. of about seconds, a neutralization number of about 10 mg. KOH/gm., a saponification number of about 95, and an iodine number of about 70; from about 0.1% to about 10% of oleic acid; and from about 0.01% to about 1% of a sodium neutralized oil soluble sulfonic acid.

4. A non-staining emulsifiable oil for the working of copper-containing non-ferrous metals consisting of a major portion of a petroleum oil; about 1% by weight of dodecyl phenyl polyether alcohol wherein said polyether alcohol group has about 24 carbon atoms; about 2% by weight of nonyl phenyl polyether alcohol wherein said polyether alcohol group has about 9 carbon atoms; about 6.7% by weight of mixed polyoxyethyl esters of mixed fatty acids wherein said polyoxyethyl groups are prepared by the polymerization of ethylene oxide and have from about 10 to about 20 carbon atoms and said mixed fatty acids have from about 16 to about 24 carbon atoms, and said esterified product has an API gravity of about 12, an SSU viscosity at 100 F. of about 175 seconds, a neutralization number of about 10 mg. KOH/gm., a saponification number of about 95, and an iodine number of about 70; about 2% by weight of oleic acid; and about 0.4% of a sodium neutralized oil soluble sulfonic acid.

References Cited in the file of this patent UNITED STATES PATENTS 1,970,578 Schoeller Aug. 21, 1934 2,470,913 Bjorkesten May 24, 1949 2,632,734 Nunn Mar. 24, 1953 2,692,859 Talley Oct. 26, 1954 FOREIGN PATENTS 733,783 Great Britain July 20, 1955 OTHER REFERENCES Ethofats, Ethomids and Ethomeens, pub. of Armour Chemical Division, Chicago, 1954, page 16. 

1. A NON-STAINING EMULSIFIABLE OIL FOR THE WORKING OF COPPER-CONTAINING NON-FERROUS METALS CONSISTING OF A MAJOR PORTION OF A HYDROCARBON OIL; FROM ABOUT 0.1% TO ABOUT 10% BY WEIGHT OF AN ALKYL ARYL POLYETHER ALCOHOL, WHEREIN SAID ALKYL GROUP HAS FROM ABOUT 8 TO ABOUT 16 CARBON ATOMS AND SAID POLYETHER ALCOHOL GROUP HAS FROM ABOUT 8 TO ABOUT 40 CARBON ATOMS; FROM ABOUT 0.1% TO ABOUT 15% BY WEIGHT OF A POLYOXYETHYL ESTER OF UNSATURATED FATTY ACID, WHEREIN SAID POLYOXYETHYL GROUP HAS FROM ABOUT 8 TO ABOUT 24 CARBON ATOMS AND SAID UNSATURATED FATTY ACID HAS FROM ABOUT 16 TO ABOUT 24 CARBON ATOMS; AND FROM ABOUT 0.1% TO ABOUT 10% WEIGHT OF OLEIC ACID.
 2. THE COMPOSITION OF CLAIM 1 HAVING INCLUDED THEREIN FROM ABOUT 0.01% TO ABOUT 1% OF AN OIL SOLUBLE SULFONIC ACID HAVING AN ALKALI METAL CONSTITUENT 